Catalytic rearrangement of acetylenic carbinois to a {60 ,{62 -unsaturated carbonyl compounds

ABSTRACT

Process for converting secondary and tertiary acetylenic carbinols to the corresponding -unsaturated carbonyl compounds by rearranging the carbinol in the presence of a (trilower alkyl-, tricycloalkyl-, triphenyl- or triphenyl-lower alkyl-siloxy)vanadium oxide catalyst.

United States Patent 11 1 Pauling 1 1 CATALYTIC REARRANGEMENT OFACETYLENIC CARBINOIS TO A a,B-UNSATURATED CARBONYL COMPOUNDS {751Inventor; Horst Pauling. Bottmingen.

Switzerland 173] Assignee: Hoffmann-La Roche Inc., Nutley.

22 Filed: Apr. 27, 1972 Appl. No: 248,046

{30] Foreign Application Priority Data Switzerland ..6750/72 Switzerland..3564/72 May 7.1971 Mar. 10.1972

[52] 11.5. C1. 260/340); 260/478 R; 260/488 F; 260/488 H; 260/592;260/593 R; 260/598; 260/599; 260/601 R. 260/602 R 2.853.520 9/1958Newman 260/593 R 1 1 Nov. 11, 1975 Grunchelli et a1. ooooooooooo 260/429R Cohen 260/429 R FOREIGN PATENTS OR APPLICATIONS 1.554.305 12/1 68France. 260/593 OTHER PUBLICATIONS JA1C.S.. v01. 59. No. l. (1937). pp.118-121.

Primary liruminer-Donzllcl G. Duus Ass/slam E.\uminrD. BY SpringerA/Im'ney. Agent. or FirmSnmue1 L. Welt: Jon S. Suxc; Richard A. Guither[57] ABSTRACT Process for converting secondary and tertiary acetyleniccarbinols to the corresponding afi-unsaturuted carbonyl compounds byrearranging the curbinol in the presence of a (trilower a1k)'l-,tricycloalkyb. triphenylor triphenyl-lower 111k 1-sil0xy)-vanuc1iumoxide catalyst.

23 Claims. No Drawings CATALYTIC REARRANGEMENT OF ACETYLENIC CARBINOISTO A a ,B-UNSATURATED CARBONYL COMPOUNDS BACKGROUND OF THE INVENTIONCertain a,B-mono-unsaturated aldehydes have heretofore been obtained bythe catalytic rearrangement of corresponding tertiary aeetyleniccarbinols or derivatives thereof. For example, acetylenic carbinols havebeen converted to unsaturated aldehydes by a process involving initiallyesterifying the carbinols and then rearranging the ester derivative withthe aid of a silver or copper catalyst. Typically, such rearrangementreactions have required several process steps, including the formationof an allene ester intermediate.

In an effort to reduce the number of process steps required for suchcatalytic rearrangement processes, catalysts derived from a metal of theVth to VIIth subgroup of the periodic chart, particularly vanadium,niobium, molybdenum, tungsten and rhenium, have been utilized instead ofcopper or silver catalysts. Such cata lysts have permitted acetyleniccarbinols to be expeditiously rearranged to unsaturated aldehydes in asingle operation.

However, the use of such catalysts of the Vth to VIIth sub-group has notbeen found to be completely satisfactory. Considerable loss of catalystactivity has been found to inevitably occur during the course of therearrangement reaction. In addition, it has been discovered thatdecomposition products are formed during the rearrangement reaction asthe catalyst loses activity and that these decomposition products causethe aldehyde product to be destroyed as it is formed, thereby reducingproduct yields.

SUMMARY OF THE INVENTION In accordance with this invention, a process isprovided for obtaining a,B-unsaturated carbonyl compounds of theformula:

wherein R, is individually hydrogen or lower alkyl; R is individuallyhydrocarbyl, cyclohydrocarbyl, or cyclohydrocarbyl substitutedhydrocarbyl; R taken together with R form a cyclohydrocarbyl; R ishydrogen, hydrocarbyl, cyclohydrocarbyl or cyclohydrocarbyl substitutedhydrocarbyl; said hydrocarbyl and cyclohydrocarbyl being unsubstitutedor substituted in one or more positions with lower alkyl, lower alkoxy,hydroxy, oxo, ketalized oxo, lower alkanoyl, aroyl, lower alkanoyloxy,or aroyloxy; comprising rearranging an acetylenic carbinol of theformula:

wherein R R and R are as above;

in the presence of a catalyst of the formula:

wherein R is lower alkyl, cycloalkyl, phenyl, or phenyl lower alkyl anyof which may be substituted by lower alkyl; R is R, or (R Si-; m is aninteger of from 1 to 3', and n is an integer of from to 2', with theproviso that the sum of m and n is 3.

By utilizing the isomerisation catalyst of formula III, catalyticactivity can be maintained during the reaction, permitting the catalystto be used in repeated, subsequent reaction batches and minimizing theproduction of decomposition products which would reduce the yields ofthe carbonyl compound of formula I.

DETAILED DESCRIPTION OF THE INVENTION As used throughout thisapplication, the term hydrocarbyl" denotes a monovalent, straight chainor branched chain aliphatic substituent consisting solely of carbon andhydrogen. The hydrocarbyl group can be saturated or unsaturated in oneor more positions. Among the hydrocarbyl groups are included alkylgroups containing from 1 to 30 carbon atoms and alkenyl and alkynylgroups containing from 2 to 30 carbon atoms which can be unsubstitutedor substituted in one or more positions with lower alkyl, lower alkoxy,hydroxy, oxo, ketalized oxo, lower alkanoyl, aroyl, lower alkanoyloxy,or aroyloxy groups. Among the preferred hydrocarbyl groups are includedlower alkyls and groups having an isoprene or isoprene-like structure.Among the preferred substituted or unsubstituted hydrocarbyl groupsdenoted by R and R are included methyl, ethyl,2,6-dimethyl-hepta-l,3,5-trienyl, 4- methylpent-Ii-enyl,4,8-dimethyl-nona-3,7-dienyl, 4,8, l Z-trimethyltridecyl,4-hydroxy-4-methyl-pentyl, and 4-methoxy-4-methylpentyl groups.

As also used throughout this application, the term cyclohydrocarbyl"denotes a monovalent, cycloaliphatic substituent consisting solely ofcarbon and hydrogen. The cyclohydrocarbyl group can be saturated orunsaturated in one or more positions. The cyclohydrocarbyl substituentdefined by R R and R, can be unsubstituted or substituted in one or morepositions with lower alkyl, lower alkoxy, hydroxy, 0x0, ketalized oxo,lower alkanoyl, aroyl, lower alkanoyloxy or aroyloxy groups. Thesubstituted and unsubstituted cyclohydrocarbyl can include from 3 to 20carbon atoms. Among the preferred cyclohydrocarbyl substituents whichare defined by R,, R and R are included cyclohexyl, cyclopropyl,cycloheptyl and cyclohexenyl. In the compounds of formula II, where Rand R are joined together to form an unsubstituted or substitutedcyclohydrocarbyl substituent, the preferred compounds are:

l-ethynyl-cyclohexanol,

4-ethynyl-4-hydroxyl-oxo-3 ,5 ,S-trirnethylcyclohex-2-ene, and

4-ethyn yl-Lhydroxyl l -ethylenedioxy-3,5,S-trimethylcyclohex-2ene.

As further used throughout this application, the term cyclohydrocarbylsubstituted hydrocarbyl" denotes cyclohydrocarbyl substitutedhydrocarbyl groups wherein cyclohydrocarbyl and hydrocarbyl are definedas above. Both the cyclohydrocarbyl and hydrocarbyl groups can beunsubstituted or either one or both of the hydrocarbyl andcyclohydrocarbyl groups can be substituted in one or more positions withlower alkyl, lower alkoxy, hydroxy, oxo, ketalized oxo, lower alkanoyl,aroyl, lower alkanoyloxy or aroyloxy. Among the preferredcyclohydrocarbyl substituted hydro carbyl substituents defined by R andR are the groups wherein the hydrocarbyl moiety has an isoprene orisoprenelike structure, such as 2-( 2,6,o-trimethyl-cyclohex- 1 -enl -yl)-vinyl',

2-( 4-oxo-2,6,6-trimethyl-cyclohexl-enl 'yl )-vinyl;

2-( 4,4-ethylenedioxy-2,6,6-trimethyl-cyclohex- 1 -enl-yl)-vinyl;

6(2,6,6-trimethyl-cyclohex- 1 -en- 1 -yl )-4-methyl-hexa-l,3,5-trienyl;

6-(4-oxo-2,6,6-trimethy1-cyclohex- 1 -en- 1 -yl )-4-methyl-hexa-1,3,5-trienyl; and

6-(4,4-ethylenedioxy-2,6,6-trimcthyl-cyclohex-l-enl-yl )-4-methyl-hexa l,3,5-trienyl groups.

As further used throughout this application, the term lower alkylcomprehends branched chain and straight chain, saturated aliphatichydrocarbyl groups containing l to 7 carbon atoms, such as methyl,ethyl, propyl and isopropyl. As also used herein, the term lower alkoxycomprehends lower alkyloxy groups containing 1 to 7 carbon atoms such asmethoxy and isopropoxy. As further used herein, the term lower alkanoyl"comprehends lower alkyl acyl groups containing l to 6 carbon atoms suchas formyl, acetyl, propionyl, and butyryl. As still further used herein,the term aroyl comprehends monocyclic, aromatic hydrocarbon acyl groupswhich may be unsubstituted or substituted in one or more positions witha lower alkylenedioxy, lower alkyl, halogen, nitro or lower alkoxy. Thepreferred aroyl is benzoyl. Also herein, the term lower alkanoyloxycomprehends lower alkyl acyloxy groups containing 1 to 6 carbon atomssuch as acetoxy and propionyloxy. Further herein, the aroyloxycomprehends groups such as benzoyloxy. Still further herein, the termcycloalkyF comprehends cycloaliphatic groups of 3 to 6 carbon atoms,such as cyclohexyl. Also herein, the term phenyP comprehendsunsubstituted phenyl.

As still further used throughout this application, the term aliphatic",with reference to a hydrocarbyl or cyclohydrocarbyl group, denotessubstituents containing no aromatic unsaturation but which can beotherwise saturated or unsaturated i.e. an alkyl or a group containingolefinic and/or acetylenic unsaturation. Also herein, the term ketalizedoxo comprehends derivatives of an oxo group formed by reaction thereofwith a lower alkanediol, preferably ethylene glycol, or a lower alkanol,preferably methanol, to yield a lower alkylenedioxy group. The preferredlower alkylenedioxy groups are the groups having 1 to 4 carbon atoms,particularly methylenedioxy and ethylenedioxy.

In accordance with the process of this invention, an acetylenic carbinolof formula ll is rearranged in the presence of a catalyst of formula lllto an afiunsaturated carbonyl compound of formula 1. Preferably, therearrangement is carried out by heating the carbinol in the presence ofthe catalyst. ln carrying out this process, the catalyst is preferablypresent in an amount of about 0.1 to 5.0 mol percent based on thecarbinol substrate, with 1.5 to about 2.0 mol percent of the catalystbeing especially preferred.

This rearrangement reaction is preferably carried out in an inertorganic solvent. ln carrying out this reaction, any conventional inertorganic high-boiling solvent can be utilized. Among the preferredsolvents are included aliphatic hydrocarbons, particularly heptane,cyclohexane, cyclododecane, decalin, paraffin and paraffin oil; aromatichydrocarbons, particularly benzene, nitrobenzene, toluene and xylene;halogenated hydrocarbons, particularly chlorobenzene; ethers,particularly anisole and dioxane; and amines, particularly N-mcthylaniline. Polymeric silicon-containing solvents are also useful,especially silicon oils containing aliphatic or aromatic groups,particularly methyl phenyl polysiloxane.

ln carrying out this rearrangement reaction, temperature and pressureare not critical, and this reaction can be suitably carried out at atemperature of between about room temperature (22C.) and the boilingpoint of the reaction mixture and at atmospheric pressure. Preferably,the reaction is carried out at a temperature between 50C. and 200C, witha temperature of about 100 to l60C. being particularly preferred. Ifdesired, the isomerization can also be carried out under pressure, inwhich case pressures up to about 50 atmospheres can be used.

The time for this reaction can vary within wide ranges. In general, itis preferred to utilize about 2 to 20 hours for the reaction. Also, thisreaction can be carried out in the presence of or with the exclusion ofair.

The afi-unsaturated carbonyl compound of formula I, which is obtained asthe product of the rearrangement reaction of this invention, can beseparated from the unreacted portions of the acetylenic carbinolstarting material in a well known manner, preferably by rectitication.The unreacted carbinol portions can be cycled to the next batch. Withthis procedure, there are obtained, in general, conversions of to and,depending on the carbinol starting material employed, yields of morethan based on the reacted carbinol.

Among the important a,B-unsaturated carbonyl compounds of formula I areincluded compounds of the formula:

wherein R. and R' are taken together to form an unsubstitutedcyclohydrocarbyl or a cyclohydrocarbyl substituted with lower alkyl,lower alkoxy, hydroxy, oxo or ketalized oxo; compounds of the formula:

wherein R; is hydrogen or lower alkyl; a l, b l andc= l ora=0,b= l andc=1 ora=(),h=()

and c l or a O, b O and c (l; and the dotted a 11B bonds can beoptionally hydrogenated and wherein 5 hydroxy and lower alkoxysubstituents may be OH present:

and compounds of the formula: wherein R" is as above;

wherein R';,, a, b, c and the dotted bonds are as above; and whereinhydroxy and lower alkoxy substituents may be present;

2, W so wherein d is an integer of 0 to l; X is hydroxy or hy- H drogen;and Y and Z are hydrogen or taken together oxo. Y Z d In accordance withthe rearrangement reaction of this invention, among the particularlyimportant afiunsaturated carbonyl compounds of formula l are in- Amongthe acetylenic carbinols of formula [I are included the followingimportant cyclohydroearbyl eluded: compounds:

cyclohexylidene acetaldehyde; y y y I(4,4-ethylenedioxy-2,6,6-trimethyl-cyclohex-Z-enl y' ,5 y

cyclohex-Z-ene; and

l'dene -acetaldeh de; y I y 4-ethyn yl-4-hydroxyl l-ethylenedioxy-3,5,5-trimecinnamaldehyde;

2-methyl-hept-2-en-4-one; thylcyclohex'z'enei senecioaldehyde; as wellas the following acyclic hydrocarbyl comcitral; Pounds:

40 dehydrolinalool;

3-hydroxy-3-methyl-but- 1 -yne; 3-hydroxy-3 ,7,l l-trimethyl-dodeca-6,lO-dien-1-yne; and

7-methoxy-dehydrolinalool.

The catalysts of formula lll can be prepared according to known methods.The catalysts can be prepared, for example, according to one of thefollowing procedures:

i. the reaction of, for example, vanadium pentoxide with, for example, atrialkyl silanol of the formula [alkylh-SiOH or a triphenyl silanol ofthe formula [phenylI SiOH with azeotropic removal of the water formed inthe reaction with the aid of an entraining agent such as, for examplebenzene;

ii. the reaction of, for example, vanadium oxytrichloride with, forexample, a trialkyl silanol or triphenyl silanol in the presence of abase such as pyridine or ammonia;

iii. the reaction of, for example, vanadium oxytrichloride with, forexample, a trialkyl alkali silanolate of the formula [alkyl] SiOMe(l) ora triphenyl alkali silanor 1 late of the formula [phenyl] SiOMe(l);

iv. the reaction of, for example, a vanadium acid 1 ester of the formula[alkoxy] -V=O with, for example, & a trialkyl silanol or triphenylsilanol, if desired in the presence of catalytic amounts of an alkylorphenyl al- OH kali silanolate (eg. a trialkyl alkali silanolate);

v. the reaction of, for example, silver orthovanadate of the formula AgVO with for example, a trialkyl silyl wherein 'i and 'z are 35 above;halide of the formula [alkyl] SiCl or a triphenyl silyl7-hydroxy-citral',

7-methoxy-citral;

farnesal;

B-C, -aldehyde; and

vitamin A aldehyde.

Among the catalysts of formula Ill, preferred are the compounds whereinR is lower alkyl (particularly methyl, ethyl, isopropyl or n-butyl),phenyl, tolyl or xylyl, or unsubstituted phenyl lower alkyl(particularly benzyl or phenethyl). Among the preferred catalysts,particularly preferred are the compounds of formula [II wherein m is 3and n is 0, quite particularly tris- [trimethyl-siloxy]-vanadium oxideand tris-[triphenylsiloxy]-vanadium oxide.

The acetylenic carbinols of formula II utilized as starting materials inthe process of this invention for conversion to the preferred carbonylcompounds of formulae lA, lB, [C and ID, hereinbefore, are compounds ofthe formulae:

7 halide of the formula [phenylhSiCl in a solvent such as, for example,benzene or methylene chloride;

vi. the reaction of, for example, vanadium pentoxide with, for example,a hexaalkyl disiloxane of the formula [alkyl] SiOSi[alkyl] at anelevated temperature, for example, at about 100C; and

vii. the double reaction of a vanadium acid ester of the formula[alkoxy] -V=O with a trialkyl silyl ester or triphenyl silyl ester, forexample, of tripropyl orthovanadate with trimethyl silyl acetate withthe expulsion of propyl acetate.

1n accordance with the rearrangement reaction of this invention, it hasbeen found that the activity of the catalyst of formula [11 is retainedduring the reaction, permitting the catalyst to be cycled to subsequentbatches for repeated use. It has also been found that the particularlypreferred catalysts of formula 111, wherein "i=3, provide surprisinglyhigher yields of and higher conversions to the afi-unsaturated carbonylcompound than is provided by catalysts heretofore used. In addition,these particularly preferred catalysts retain their activity over manybatches and form practically no decomposition products which interferewith the yields of a,B-unsaturated carbonyl compound of for mula l.

The examples which follow further illustrate this in vention.

The silicon oil employed in the Examples 3, 7 and 13 has a boiling pointof l50"C/10 mm Hg and a density of d of 0,975.

The paraffin oil employed in the Examples -14 has a boiling point ofl70"C/l0 mm Hg.

EXAMPLE 1 A mixture of 15.2 g of 3-hydroxy-3,7-dimethyl-octa- 6-en1-yne(dehydrolinalool), 0.52 g of tris-[trimethylsiloxy]-vanadium oxide and750 g of liquid paraffin [boiling point 170/0.l mmHg] is stirred at 125Cfor hours in a dry atmosphere. The 3,7-dimethyl-2,6- octadienal (citral)formed is thereafter separated from the unreacted linalool byrectification. The conversion of the dehydrolinalool employed amounts to11.7 g, corresponding to 77%. The yield of citral is 11.25 g,corresponding to 96% conversion based on reacted dehydrolinalool.

EXAMPLE 2 15.2 g of dehydrolinalool, 2 g oftris-[triphenylsiloxy]-vanadium oxide and 85 ml of high-boiling paraffinoil ((1 0.885) are stirred at 140C. for 3.5 hours in the absence ofmoisture. The citral formed is thereafter separated by rectification.10.5 g (69.2%) of dehydrolinalool react with the formation of 9.3 g ofcitral. The yield of citral amounts to 88.5% based on reacteddehydrolinalool. After distillation of all material which is liquidbelow 50C/ 10' mmHg, fresh dehydrolinalool can be added periodically tothe solution of the catalyst in paraffin oil and reacted in the mannerdescribed earlier. Even after employing the foregoing catalyst system onthree batches, its catalytic activity does not fall off to anyappreciable extent, repeated comparable results being obtainable.

EXAMPLE 3 15.2 g of dehydrolinalool and 0.6 g oftris-[dimethylethyl-siloxy]-vanadium oxide are heated to 130C for 5hours in 300 ml of silicon oil. The citral formed is then separated byrectification. The conversion of 8 dehydrolinalool amounts to 11.3 g,corresponding to 74.3%. The yield of citral is 9.7 g, corresponding toan 85.8% conversion based on reacted dehydrolinalool.

EXAMPLE 4 15.2 g of dehydrolinalool, 1.06 ofbis-[triphenylsiloxy]-[trimethyl-siloxy]-vanadium oxide and 150 ml ofsilicon oil are heated to C for 3 hours while stirring in an inert gasatmosphere. The citral formed is then separated by rectification. Theconversion of the dehydrolinalool employed amounts to 10.9 g,corresponding to 71.7%. The yield of citral is 9.7 g, corresponding to89% conversion based on reacted dehydrolinalool.

EXAMPLE 5 15.2 g of dehydrolinalool, 1.5 g ofbis-[trimethylsiloxy]-[triphenyl-siloxyl-vanadium oxide and ml ofnitrobenzene are heated to 150C. for 2 hours with the exclusion ofmoisture. The citral formed is then separated by rectification. Theconversion of dehydrolinalool employed amounts to 1 1.1 g, correspondingto 73%. The yield of citral is 9.4 g, corresponding to 84.6% conversionbased on reacted dehydrolinalool.

EXAMPLE 6 15.2 g of dehydrolinalool, 1 g ofbis-[triphenylsiloxyl-isopropoxy-vanadium oxide and 90 ml ofhigh-boiling paraffin oil (c1 0.885) are heated at 125 for 10 hours withthe exclusion of moisture. The citral formed is separated byrectification. The conversion of dehydrolinalool employed amounts to 9.5g, corresponding to 62.5%. The yield of citral is 8.1 g, correspondingto 85.3% conversion based on reacted dehydrolinalool.

EXAMPLE 7 15.2 g of dehydrolinalool, 0.92 g of[triphenyl-siloxy]-bis-[isopropoxyl-vanadium oxide and ml of silicon oilare heated to 125C for 6 hours with the exclusion of moisture. Thecitral formed is separated by rectification. The conversion ofdehydrolinalool employed amounts to 7 g, corresponding to 46%. The yieldof citral is 5.75 g, corresponding to 82.2% conversion of reacteddehydrolinalool.

EXAMPLE 8 8.4 g of 3-hydroxy-3-methyl-but-1-yne, 1 g of tris-[trimethyl-siloxy]-vanadium oxide and 50 ml of highboiling paraffin oil(d 0.885) are stirred at l 10C. for 30 hours with the exclusion ofmoisture. The 3- methylbut-Z-en-al formed is then separated byrectification. The conversion of the acetylenic carbinol employedamounts to 5.9 g, corresponding to 70.3%. The yield of3-methyl-but-2-en-l-al is 5.4 g, corresponding to 91.5% conversion ofthe reacted acetylenic carbinol.

EXAMPLE 9 the reacted acetylenic carbinol.

EXAMPLE 10 29.4 g of 3-hydroxy-3,7,l1,1S-tetramethyl-hexadccl-yne, 0.75g of tris-[trimethyl-siloxyl-vanadium oxide and 500 ml of high-boilingparaflin oil are heated to 125C. for 8 hours with the exclusion ofmoisture. The 3,7,1 1,l-tetramethyl-hexadec-Z-en- 1 -al formed isseparated by rectification. The conversion of the acetylenic carbinolemployed amounts to l 1.3 g, corresponding to 38.4% The yield of 3,7,]1,1 S-tetramethylhexadec-2-en-1-a1 is 9.1 g, corresponding to 80.5%conversion of reacted acetylenic carbinol.

EXAMPLE 1 1 18.4 g of 3-hydroxy-7-methoxy-3,7-dimethyl-oct-l yne(7-methoxy-dehydrolinalool). 0.7 g of tris- [trimethyl-siloxy]-vanadiumoxide and 150 ml of highboiling paraffin oil are stirred at 125C for 7hours with the exclusion of moisture. The7-methoxy-3,7-diinethyl-oct-2-en-l-al formed is separated byrectification. The conversion of the acetylenic carbinol employedamounts to l 1.6 g, corresponding to 63%. The yield of7-methoxy-3,7-dimethyl-oct-2en-l-al is 10.8 g. corresponding to 93.2%conversion of reacted acetylenic carbinol.

EXAMPLE 12 12.4 g of l-ethynyl-l-cyclohexanol, 2 g of tris-[triphenyl-siloxyl-vanadium oxide and 100 ml of highboiling paraffin oilare heated to 130C for 6 hours with the exclusion of moisture. Theconversion of the acetylenic carbinol employed amounts to 8.9 g,corresponding to 71.7%.

The following two isomerization products are isolated from this reactionby rectification:

cyclohexylidene-acetaldehyde (I) b.p. 88C/ 13 mm Hgcyclohex-l-en-l-yl-acetaldehyd (l1) b.p. 82C/l3 mm Hg. The total yieldof I and 11 is 7.8 g, corresponding to 87.6% conversion of the reactedl-ethynyl-l-cyclohexanol. The molar proportion of the two resultingaldehydes I and 11 to one another is 38.4:61.6.

EXAMPLE 1 3 13.2 g of 3-hydroxy-3-phenyl-prop-l-yne, 2 g of tris-[triphenyl-siloxyl-vanadium oxide and 100 ml of silicon oil are heatedto 140C for 6 hours with the exclu' sion of moisture. The cinnamaldehydeformed is separated by rectification. The conversion of the acetyleniccarbinol employed amounts to 12.1 g, corresponding to 91.6%. The yieldof cinnamaldehyde is 1 1.4 g, corre sponding to 94.3% conversion of thereacted 3- hydroxy-3-phenyl-pr0p- 1 -yne.

EXAMPLE 14 12.6 g of 2-hydroxy-2-methylhept3-yne. 0.7 g oftris-(trimethyl-siloxy]-vanadium oxide and 150 ml of high-boilingparaffin oil are heated at 130C for 5 hours with the exclusion ofmoisture. The 2-metliy1-hept-2 en-4-one formed is separated byrectification. The conversion of the acetylenic carbinol employedamounts to 11.6 g, corresponding to 92%. The yield of2-methylhept-2-en-4-one is 1 1.0 g, corresponding to 94.8% conversion ofthe reacted acetylenic carbinol.

EXAMPLE 15 10 g of4-ethynyl-4-hydroxy-l,1-ethylenedioxy-3,5,5-trimethyl-cyclohcx-2-ene. 0.15 g of hydroquinone, 0.02 ml oftris-[trimethyl-siloxyl-vanadium oxide and 100 ml of dry mcsitylene areheated to boiling under reflux conditions for 16 hours with theexclusion of moisture. The solvent is subsequently distilled off at 40Cunder reduced pressure. The residual isomer mixture of cis/traus(4.4-cthylenedioxy-2,6,6-trimethylcyclohexJ-cn- Lylidenc l-acctaldehydeboils at l 10125(/0. 1 rnmHg after rectification in a high vacuum. Theconversion of the acetylenic carbinol employed amounts to 8 g,corresponding to The aldchyde product is obtained in a yield of 7.2 g,corresponding to 91 1% conversion of the reacted acetylenic carbinol.

EXAMPLE 16 800 m1 of liquid ammonia are conducted into a 2 liter3-necked flask which is provided with a mechanical stirrer. droppingfunnel and Claisen head having a dryice cooler. 10 g of lithium are thenintroduced into the flask within 30 minutes while stirring. The mixtureis stirred for 60 minutesv Sufficient acetylene is passed pouredcautiously onto a mixture of ice and 400 ml of a 25% by weight ammoniumchloride solution. The ether phase is separated, washed with water,dried over sodium sulphate, filtered and evaporated under reducedpressure. The residual crystalline 4-ethynyl-4- hydroxyl,1-ethy1enedioxy-3.5,S-trimethyl-cyclohex- 2-ene melts at -86C afterrecrystallization from ethyl acetate/petroleum ether.

1 claim:

1. In a process for obtaining alpha,beta-unsaturated carbonyl compoundsof the formula:

wherein R is individually hydrogen or lower alkyl having from 1 to 7carbon atoms; R is individually straight chain saturated or olefinicallyunsaturated aliphatic hydrocarbyl, cyclohydrocarbyl or cyclohydrocarbylsubstituted straight chain saturated or olefinically unsaturatedaliphatic hydrocarbyl; R taken together with R form a cyclohydrocarbyl;R is hydrogen, straight chain saturated or olefinically unsaturatedaliphatic hydrocarbyl, cyclohydrocarbyl or cyclohydrocarbyl substitutedstraight chain saturated or olefinically unsaturated alphatichydrocarbyl; said aliphatic hydrocarbyl and cyclohydrocarbyl may beunsubstituted or substituted with from 1 to 3 lower alkyl groups havingfrom 1 to 3 carbon atoms, and from zero to 1 substituents selected fromthe group consisting of lower alkoxy 11 having from l to 7 carbon atoms,hydroxy, oxo, oxo ketalized with ethylene glycol, lower alkanoyl of from2 to 6 carbon atoms, benzoyl, lower alkanoyloxy having from 2 to 6carbon atoms, or benzoyloxy; wherein said aliphatic hydrocarbyl grouphas from i to 30 carbon atoms and said cyclohydrocarbyl group has from 4to 20 carbon atoms; by rearranging in an inert organic solvent medium anacetylenic carbinol of the formula:

wherein R R and R are as above; the improvement which comprises carryingout said rearrangement, in the presence of a catalyst of the formula:

wherein R is lower alkyl, cyclohexyl, phenyl or phenyl lower alkyl, anyof which may be substituted by lower alkyl; R is R or (R Si-; m is aninteger of from 1 to 3; and n is 0, l or 2; with the proviso that thesum of m and n is 3; and the lower alkyl group has from 1 to 7 carbonatoms; and at a temperature of from 22C. to the boiling temperature ofthe reaction medium.

2. The process of claim I wherein said catalyst is of the formula:

wherein R, m and n are as above and R is lower alkyl, phenyl orunsubstituted phenyl lower alkyl.

3. The process of claim 2 wherein said catalyst is of the fonnula:

4. The process of claim 3 wherein said catalyst is tris-[trimethyl-siloxy]-vanadium oxide or tris-[triphenysiloxy1-vanadiumoxide.

5. The process of claim 1 wherein said process is carried out at atemperature of lOC. to 160C.

6. The process of claim 1 wherein said process in carried out in ahydrocarbon or silicon oil.

7. The process of claim I wherein said catalyst is present in an amountof 0.1 to 5.0 mol percent based on the carbinol substrate.

8. The process of claim 7 wherein said catalyst is present in an amountof about L to 2.0 mol percent.

9. The process of claim I wherein said carbinol is a compound of theformula:

wherein R and R' are taken together to form an unsubstitutedcyclohydrocarbyl or a cyclohydrocarby] substituted with lower alkyl,lower alkoxy, hydroxy. 0x0, or ketalized mm. 10. The process of claim 9wherein said carbinol is l -ethynyl-cyclohexanol. 15 II. The process ofclaim 9 wherein said carbinol is 4-ethynyl-4-hydroxyl l-ethylenedioxy-3,5,5-trimethylcyclohex-Z-ene.

12. The process of claim I wherein said carbinol is a compound of thefonnula:

R112 &

15. The process of claim 14 wherein said carbinol is6-hydroxy-6-methyl-hept-4-yne.

l6. The process of claim 14 wherein said carbinol is 3-hydroxy-3,7,l 1,l S-tetramethyl-hexadecl -yne.

17. The process of claim 14 wherein said carbinol is 3-hydroxy-3,7,ll-trimethyl-dodeca-o, l0-dienl -yne.

18. The process of claim 14 wherein said carbinol is3-hydroxy-3,7-dimethyl-oct-6-enl -yne.

19. The process of claim 14 wherein said carbinol is3-hydroxy-7-methoxy3 ,ldimethyl-oct- 1 -yne.

20. The process of claim 14 wherein said carbinol is3-hydroxy-3-methyl-butl -yne.

21. The process of claim 14 wherein said carbinol is 3,7-dihydroxy-3,7-dimethyl-octl -ynei 22. The process of claim I wherein saidcarbinol is a compound of the formula:

wherein d is an integer of O to l; X is hydrogen or hydroxy; and Y and Zare hydrogen or taken together oxo.

-(2,6,6-trimethyl-cyclohex- 1 -en- 1 -yl )-3-hydr0xy-3-methylpenta-4-enl-yne.

1. IN A PROCESS FOR OBTAINING ALPHA,BETA-UNSATURATED CARBONYL COMPOUNDSOF THE FORMULA:
 2. The process of claim 1 wherein said catalyst is ofthe formula:
 3. The process of claim 2 wherein said catalyst is of theformula: ((R''4)3-Si-O)3-V O wherein R''4 is as above.
 4. The process ofclaim 3 wherein said catalyst is tris-(trimethyl-siloxy)-vanadium oxideor tris-(triphenysiloxy)-vanadium oxide.
 5. The process of claim 1wherein said process is carried out at a temperature of 100*C. to 160*C.6. The process of claim 1 wherein said process in carried out in ahydrocarbon or silicon oil.
 7. The process of claim 1 wherein saidcatalyst is present in an amount of 0.1 to 5.0 mol percent based on thecarbinol substrate.
 8. The process of claim 7 wherein said catalyst ispresent in an amount of about 1.5 to 2.0 mol percent.
 9. The process ofclaim 1 wherein said carbinol is a compound of the formula:
 10. Theprocess of claim 9 wherein said carbinol is 1-ethynyl-cyclohexanol. 11.The process of claim 9 wherein said carbinol is4-ethynyl-4-hydroxy-1,1-ethylenedioxy-3,5,5-trimethylcyclohex-2-ene. 12.The process of claim 1 wherein said carbinol is a compound of theformula:
 13. The process of claim 12 wherein said carbinol is3-hydroxy-3-phenyl-prop-1-yne.
 14. The process of claim 1 wherein saidcarbinol is an unsubstituted compound of the formula:
 15. The process ofclaim 14 wherein said carbinol is 6-hydroxy-6-methyl-hept-4-yne.
 16. Theprocess of claim 14 wherein said carbinol is3-hydroxy-3,7,11,15-tetramethyl-hexadec-1-yne.
 17. The process of claim14 wherein said carbinol is3-hydroxy-3,7,11-trimethyl-dodeca-6,10-dien-1-yne.
 18. The process ofclaim 14 whErein said carbinol is 3-hydroxy-3,7-dimethyl-oct-6-en-1-yne.19. The process of claim 14 wherein said carbinol is3-hydroxy-7-methoxy-3,7-dimethyl-oct-1-yne.
 20. The process of claim 14wherein said carbinol is 3-hydroxy-3-methyl-but-1-yne.
 21. The processof claim 14 wherein said carbinol is3,7-dihydroxy-3,7-dimethyl-oct-1-yne.
 22. The process of claim 1 whereinsaid carbinol is a compound of the formula:
 23. The process of claim 22wherein said carbinol is5-(2,6,6-trimethyl-cyclohex-1-en-1-yl)-3-hydroxy-3-methylpenta-4-en-1-yne.